基于QuEChERS-超高效液相色谱-串联质谱法测定树莓中乙基多杀菌素残留

Determination of Spinetoram Residues in Raspberry by QuEChERS-Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

目的:建立超高效液相色谱-串联质谱法定量测定树莓中乙基多杀菌素-J(XDE-175-J)和乙基多杀菌素-L(XDE-175-L)残留的分析方法。方法:样品经乙腈提取,乙二胺-N-丙基硅烷和石墨化碳黑净化,超高效液相色谱C18反向色谱柱分离,以乙腈和0.1%甲酸(含2 mmol·L^(-1)乙酸铵)为流动相进行梯度洗脱,采用电喷雾正离子的多反应离子监测模式,基质匹配标准溶液外标法定量。结果:乙基多杀菌素-J(XDE-175-J)在0.0375~7.5000μg·L^(-1)呈现出良好的线性关系(R2=0.9993),检出限为0.025μg·kg^(-1),定量限为0.075μg·kg^(-1),在0.15μg·kg^(-1)、0.75μg·kg^(-1)、1.50μg·kg^(-1)3个添加水平下的日内平均回收率为97.8%~105.5%,日内变异系数为4.1%~8.6%;日间平均回收率为96.3%~108.3%,日间变异系数为2.8%~9.7%;乙基多杀菌素-L(XDE-175-L)在0.0125~2.5000μg·L^(-1)呈现出良好的线性关系(R2=0.9992),检出限为0.008μg·kg^(-1),定量限为0.025μg·kg^(-1),在0.05μg·kg^(-1)、0.25μg·kg^(-1)、0.50μg·kg^(-1)3个添加水平下的日内平均回收率为92.7%~102.3%,日内变异系数为2.5%~6.3%,日间平均回收率为94.6%~99.7%,日间变异系数为3.4%~10.7%。结论:该方法简单、快速、可靠、具有良好的灵敏度、回收率和精密度,适用于树莓中痕量乙基多杀菌素的大批量快速检测及定量分析。

Objective:To establish an ultra-high performance liquid chromatography-tandem mass spectrometry method for the quantitative determination of spinetoram residues,XDE-175-J and XDE-175-L in raspberry.Method:The samples were extracted with acetonitrile,and purified with primary secondary amine and graphitized carbon black,and separated by an ultra-high performance liquid chromatography C18 reverse chromatographic column,using gradient elution with a mobile phase of acetonitrile and 0.1%formic acid in water(containing 2 mmol·L^(-1)ammonium acetate).Detected using an electrospray ionization source in the positive ion multiple reaction monitoring mode,and quantified by an external standard method using a matrix-match standard solution.Result:XDE-175-J showed a good linear relationship in the mass concentration range of 0.0375~7.5000μg·L^(-1)(R2=0.9993),the limits of detection were 0.025μg·kg^(-1),and the limits of quantitation were 0.075μg·kg^(-1).The average recoveries for XDE-175-J at the spiked levels of 0.15μg·kg^(-1)、0.75μg·kg^(-1)、1.50μg·kg^(-1),were the intra-batch(n=6)97.8%~105.5%and coefficient of variation 4.1%~8.6%,the inter-batch(n=3)96.3%~108.3%and coefficient of variation 2.8%~9.7%;XDE-175-L showed a good linear relationship in the mass concentration range of 0.0125~2.5000μg·L^(-1)(R2=0.9992),the limits of detection were 0.008μg·kg^(-1),and the limits of quantitation were 0.025μg·kg^(-1),The average recoveries for XDE-175-L at the spiked levels of 0.05μg·kg^(-1),0.25μg·kg^(-1),0.50μg·kg^(-1)were the intra-batch(n=6)92.7%~102.3%and coefficient of variation 2.5%~6.3%,the inter-batch(n=3)94.6%~99.7%and coefficient of variation 3.4%~10.7%.Conclusion:The method is simple,rapid,reliable,has good sensitivity,recovery rate and precision,and could meet the requirements for rapid detection and quantitative analysis of trace amounts of spinetoram residues in raspberry.